Process for breaking petroleum emulsions



Patented July 18, 19 44 UNITED STATES PATENT OFFICE PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote,

Keiser,

Petrolite Corporation,

University City, and Bernhard Webster Groviej,d M ssign 0., a ors to Wilmington, Del.,

a corporation of Delaware No Drawing.

Application June 15,1942,

Serial No. 447,159 8 Claims. (Cl. 252-340) rapid process for separating emulsions which have been prepared, under controlled conditions from mineral oil, such as crude petroleum and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned is of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

We have discovered glycerol so as to introduce at least three oxyalkylene radicals for each hydroxyl group, and if the product so obtained is reacted with a polybasic carboxy acid having not over eight carbon atoms, and in such a manner as to yield a fractional ester, due to the presence of at least one free carboxyl radical, one can then esterify said acidic material or intermediate product withat, least one mole of an alcoholic compound of the type herein described to give a variety of new compositions of matter which are efliclent demulsifiers for crude oil emulsions.

The compounds herein described that are used as the demulsifler of our process, may be produced in any suitable manner, but are usually manufactured by following one of two general procedures. In one of said procedures the oxyalkylated glycerol, which is, in essence, a polyhydric alcohol, is reacted with a polybasic acid so as to give an acidic material or intermediate product, which, in turn, is reacted with an alcoholic body of the kind hereinafter described, and

. momentarily indicated by the formula R1(OH) m.

Generically, the alcoholic body herein contemplated may be considered a member of the class in which m may vary from 1 to 10, although the specific significance of m in the present instance will be hereinafter indicated. The second procedure is to react an alcohol of the formula type R1(OH)m with a polybasic acid so as to produce an intermediate product, and then react said x intermediate product or fractional ester with the selected oxyalkylated glycerol.

that if one oxyalkylates Glycerol may be conveniently indicated by the following formula:

on ClHl-OH If treated with an oxyaikylating agent, and momentarily consideration will be limited to an oxyethylating agent, one may obtain an 01wethylated glycerol of the following formula type:

(C3H40).1'H CQH5OQ(CIHIO)Q'H cmiown in which the value of 12. may vary from 3 to 10 and all the values of n need not be identical. If a polybasic carboxy acid be indicated by the formula:

coon

R--COOH COOH then the acyclic reaction product of one mole of oxyethylated glycerol and one mole of a polybasic carboxy acid may be indicated by the following formula:

(CIHAO)MOOCR(C OOH)"I CrHaOt-(CzHtOLuH (ClH|o)n'H in which n" has the value of one or two. Similarly, if two moles of the polybasic acid be used,

then the compound lowing formula:

may be indicated by the fol- Likewise, if three moles of a polybasic acid are employed, the compound may be indicated by the following formula:

If a fractional ester of the kind exemplified by the three preceding formulas is reacted with one or more moles of an alcohol of the kind previously described in a generic sense as R1(QH) m,

include ethylene oxide and glycid,

then obviously, type indicated one may obtain a material of the by the following formula:

(clmon oocn 2,353,702 monomeric compounds indicated, one wbuld in reality obtain a polymer in the sense, for example, that polyethylene glycols represent. a polymer of ethylene glycol. The term "polymer" is frequently used to indicate the polymerized product derived from a monomer in which the polymer has the same identical composition as previously stated that compounds by oxyalkylating agents, without being limited to ethylene oxide.

which, although not included, strictly speaking, by the unitary structure CnHZnO, is included within the meaning-of the hereto appended claims and may be simply considered as a variant of propylene oxide, 1. e., hydroxypropylene oxide. Similarly, where a carboxylic hydrogen atom appears, it may be replaced by metal, an ammonium radical, or substituted ammonium radical, or by an organic group derived from an. alcohol, such as an allphatic alcohol, an aralkyl alcohol, or an alicyclic alcohol, It may also be converted into an amide, including a polyaminoamide. Thus, the preceding formula may be rewritten in its broader scope, as follows:

cludes the acidic hydrogen atom itself. In the above formula and hereafter, for convenience, is intended to include any hydroxyl groups that remain.

If the compounds herein contemplated are obtained under usual conditions, at the lowest temperatures, then the monomeric form is most likely to result.

The production of the compounds herein contemplated is the result of one or more esterification steps. As is well-known, esterification procedures can be carried out in various manners, but generally speaking, esterifications can be carried out at the lowest feasible temperatures by using one or several procedures. One procedure is to pass an inert dried gas through the mass to be esterified, and have present at the same time a small amount of a catalyst, such as dried HCl gas, a dried sulfonic acid, or the like. Another and better procedure, in many instances, is to employ the vapors of a suitable liquid, so as to remove any water formed and condense both the vapors of the, liquid employed and the water insuch a manner as to trap out the water and return the liquid to the reacting'vessel. This procedure is commonly employed in the arts, and for convenience, reference is madeto U. S. Patent No. 2,264,759, dated December 2, 1941, to Paul C. Jones.

Referring again to the last two formulas indicating thecompounds under consideration, it can bereadily understood that such compounds, in numerous instances, have the property of polyfunctionality. In view of this fact, where there is at least one residual carboxyl and at least one residual hydroxyl, one would expect that under suitable conditions, instead of obtaining the Suitable oxyalkylating agents. oxide, propylene oxide, butylene in which n replaces the numbers 2, 3 or 4, Z inthe monomer. m the present instance,.however, polymerization involves the splitting and loss of water so that the process is essentially selfesterification. Thus, strictly speaking, the polymeric compounds are not absolutely isomers of the monomeric compounds, but since, -for all practical purposes, they can be so indicated, and since such practiceis common in the arts concerned with materials of this type, it is so adopted here. Thus, reference in the appended claims to polymers is intended to include the self-esterification products of the monomeric compounds.

In view of what has been said, and in view of therecognized hydrophile properties of the recurring oxyalkylene linkages, particularly the oxyethylene linkage, it is apparent. that the materials herein contemplated may vary from compounds which are clearly water-solublethrough self-emulsifying oils, to materials which are balsam-like and sub-resinous or semi-resinous in nature. The compounds may varyfrom monomers to polymers, in which the unitarystructure appears a number of times, for instance, 10 or 12 times; It is to be noted that true resins, i. e., truly insoluble materials of a hard plastic nature, are not herein included. In other words, the polymerized compounds are soluble to a fairly definite extent, for instance, at least 5% in some solvents, such as water, alcohol, benzene, dichloroethyl ether, acetone, cresylic acid, acetic acid, ethyl acetate, dioxane, or the like. This is simply another way of stating that the polymerized product contemplated must be of the sub-resinous type, which is commonly referred as an A resin, or a B resin, as distinguished a C resin, which is a highly infusible, in-

Chemistry of Synthetic 862, et seq.).

as presented, it is obvious from soluble resin (see Resins (1935), pages Reviewing the form that one may obtain compounds within the scope course, be replaced by any ionizable hydrogen;

such, for example, as a metal, an ammonium radical, asubstituted ammonium atom equivalent,

radical etc. In the hereto appended claims the word polar is used in'this specific sense.

We are aware that. compounds similar to those contemplatedin the present instance maybe derived fromp'olyhydro'xylated compounds having more than three hydroxyl-groups, for -instance, they may be derived from acyclic diglycerol, triglycerol, tetraglycerol,- mixed poly glycerols, mannitol, sorbitol, various hexitols, dulcitol, pentaerythritol, sorbitan, mannitan, di-

pentaerythritol mono-ether,- and other. similar. Such particular types in which.

compounds. higher hydroxylated materials are subjected to o'xyalkylation and. then employed in the same manner as oxyalkylated glycerol, is employed in or at least one free caboxyl alcoholic bodies for the present instance, are not contemplated in this specific case, although attention is directed to the same.

Reference is also made to other oxyalkylated compounds which may be'used as reactants to replace oxyalkylated glycerol, or oxyalkylated ethylene glycol, which latter reactant is described in a copending application hereinafter referred to. The reactants thus contemplated include the type in which there is an amino or amido nitrogen atom. Particularly, when present in a low molal type of compound prior to oxyalkylation, reference being made to polyhydroxylated materials, including those having two or three hydroxyl groups, as well as those having more than three hydroxyl groups. derivatives, particularly the oxyethylated derivatives of ethyldiethanolamine, bis(hydroxyethyl) acetamide, the acetamide of tris(hydroxymethyl) aminomethane, tetrahydroxylated ethylene diamine,'etc. Compounds may also be derived from cyclic diglycerol and the like.

Furthermore, for convenience, attention is (ii-- rected to a somewhat similar class of materials which are described in U. S. Patent No. 2,295,169,

For instance, the oxyalkylated' dated September 8, 1942, to De'Groote and Keiser.

Said'patent involves the use of the same type of reactants, but is limited, among other things, to the compounds which are essentially symmetrical in nature, for instance, involving the introduction of two alcoholic residues, whereas, in the present instance, one, two, or three, or more, might be introduced.

As indicated previously, the polybasic acids employed are limited to the type having not more than eight carbon atoms, for example, oxalic, malonic, succinic, phthalic. Similarly, one may employ acids such as fumaric, glutaconic, and various others, such as citric, malic, tartaric, and the like. The selection of the particular tribasic or dibasic acid employed,is usually concerned largely with the convenience of manufacture of the finished ester, and also the price of the reactants. Generally speaking, phthalic acid or anhydride tends to produce resinous materials, and greater care must be employed if the ultimate or final product be of a subresinous type. Specifically, the preferred type of polybasic acid is such as to contain six carbon atoms or/ less. Generally speaking, the higher the temperature employed, the easier it is to obtain large yields of esterified product,

although polymerization may be stimulated.

glutaric, adipic, maleic, and

oxalic acid may be comparatively cheap, but is decomposes readily at slightly above the boiling point of water. For this reason it is more desirable to use an acid which is more resistant to pyrolysis. Similarly,'when a polybasic acid is available in the form of an anhydride, such anhydrlde is apt to produce the ester with greater case than the acid itself. For this reason, maleic anhydrlde is particularly adaptable, and also,

' everything else considered, the cost is comparatively low on a per molar basis, even though somewhat higher on a per bound basis. Succinic acid or the anhydride has many attractive qualities of maleic anhydride, and this is also true of adipic acid. For purposes of brevity, the bulk of the examples, hereinafter illustrated, will refer to the use of maleic anhydride, although it is understood that anyother suitable polybasic acid may be employed. Furthermore, reference is made to derivatives obtained by oxyethylatiom' although, as previously pointed out, other oxyalkylating agents may be employed.

.As far as the range of oxyethylated glycerols employed as reactants is concerned, it is our preference to employ'those in which approximately 15 to 24 oxyethylene groups have been introduced into a single glycerol molecule. This means that approximately fiveto eight oxyethylene radicals havebeen introduced for each original hydroxyl group.

The oxyalkylation of glycerol is a well known procedure (see Example 11 of German Patent No 605,973, dated November 22, 1934, to I. G. Farbenindustrie' Akt, Ges.). The procedure indicated in the following three examples is substantially identical with that outlined in said aforementioned German patent.

OXYETHYLATED GLYCEROL Example 1 184 pou As of glycerol is mixed with /z%, by weight, of caustic soda solution, having a specific gravity of 1.383. The caustic soda acts as a catalyst. The ethylene oxide is added in relatively small amounts, for instance, about 44 pounds at a time. The temperature employed is from -180 C. Generally speakin the gauge pressure during the operation approximates 200 pounds at the maximum, and when reaction is complete, drops to zero, due to complete absorption of the ethylene oxide. When all the ethylene oxide has been absorbed and the reactants cooled, a second small portion, for instance, 44 more pounds of ethylene oxide, are added and the prooedure repeated until the desired ratio of 15 pound moles of ethylene oxide .to one pound mole of glycerol is obtained. This represents 660 pounds of ethylene oxide for 92 pounds of glycerol.

Oxrrrnvmrsp GLY CEROL Example 2 Otherwise, the same procedure is followed as in Example 1, preceding.

OxYErHxnArsn Gnxcenor. Example 3 The same procedure is followed as in the two previous examples, except that the ratio of ethylene oxide to glycerol is increased to 21 to one.

OXYE'IHYLATEB Gmzcsaor. MALEATE Example 1 7 One pound mole of oxyethylated glycerol (1 to 15 ratio) prepared in the manner previously described is treated with one pound mole of malelc anhydride and heated at approximately 1l 0- C. for approximately thirty minutes to two hours, with constant stirring, so as to yield a monomaleate.

OXYE'IHYLATED Gucaaor. Muslim Example 2,

The same procedure is followed as in the preceding example, except that two moles of maleic anhydride are employed so as to obtain the dimaleate instead of the monomaleate.

The same procedure is followed as in the two I preceding examples, except that three moles of maleic anhydride are employed so. as to obtain the trimaleate.

() xnrnnarsn .GLYCEROL MALEATE i Example 4 The same procedure is employed as in the preceding examples, except that oxyethylated glycerol (ratio 1 to 18) is substituted in place of oxyethylated glycerol (ratio 1 to 15) OXYETHYLATED GLYCEROL MALEATE Example 5 The same procedure is employed as in the pre-' ceding examples, except that oxyethylated glycerol- (ratio 1 to 21) is employed instead of oxyethylated glycerol (ratio 1 to or (1 to 18) Previous reference coholic body which has been defined generically by' the formula R1 (OH) m. The sub-generic class of alcoholiccompounds employed as reactants in the manufacture of the present compounds, are

watereinsoluble hydroxylated esters of polyhydric alcohols, characterized by being derived fro... high molal hydroxy acids and also by the fact that there is no residual hydroxyl radical attached to the alcohol residue, i. e., the compounds are neutral or complete esters, as differentiated from fractional esters.

Still another variety is illustrated, by the ether type of glycol, such as diethylene glycol, dibutylene lycol. etc. It is not intended to include ether alcohols, particularly ether glycols, in which the ether linkage occursmore than four times. Dihydric alcohols are also obtained by dehydroxylation of glycerol 01' the like, as, for example, by etherization with a monohydric alcohol; for instance, the methyl'ether, ethyl ether, propyl ether, butyl ether, and similar alkoxy derivatives of glycerol. Trihydric alcohols are illustrated most advantageously by glycerol. Similarly, etheriza tion with nionohydric alcohols yields trihydric alcohols from products such taerythritol, mannitan, sorbitan, etc. ether, butyl ether, or other alkoxy derivatives of diglycerol is an additional illustration of this particular type. Alcohols containing four hydroxyls may be illustrated by diglycerol, pentaerythritol,

.sorbitan,mannitan, etc.

polyhydric .alcohols just described are The este'rized with or converted by any suitable means has been made to an' al-.

as diglycerol, pen- The ethyl into water-insoluble esters of high molal hydroxy carbon atomsand not acids having at leastxll Th'e commonest in excess of 36 carbon atoms.

example of a high molal hydroxy v acid. Otherhydroxy fatty acids include hydroxystearic acid, dihydroxystearic' acid, diricinoleic acid, aleuritic acid, and the like. 7 Similar acids are obtainedin the oxidation of paraflin, petroleum hydrocarbons, or wax, and are commonly referred to as hydroxylated wax acids. Hydroxyacid is ricinoleic lated wax acids occur as by-products in the oxidation of waxes or similar materials and are usually separated o that the commonest commercial form of oxidized. wax acids represent mixtures comparatively free from the hydro'xylated compounds.- Hydroxylated acids are produced by other procedures, such as chlorination, either by addition or substitution, as, for example, chlorination of oleic acid or stearic acid. Subsequent resaturated V thereof,

bromocapric acid, alpha-bromolauric acid,

d rolyzed so acids Of actions involve the the introduction of eylenic acid, derived from castor oil, has been converted into a hydroxy undecenoic acid. Un-

preparation of materials of contemplated; Naturally-occurring naphthenic acids can also be converted into hydroxylated products by following similar procedure. An unhydroxy acid, such as ricinoleic acid, can be converted into a hydroxylated arylstearic acid. Such procedure contemplates reactions such a those involving ricinoleic acid, benzene,

having at least 11 carbon atoms and not in excess of 36 carbon atoms. kind herein contemplated as reactants to furnish the alcoholiform hydroxy].

Hydroxy acids of the kind herein may also be prepared by the hydrolysis of alphahalogen acid For instance, alpha-bromocaproic acid, alpha-bromocaprylic acid, alphaalphacontemplated bromomyristic acid, and the like, can be hydrolyzed to give the corresponding alpha-hydroxy acid. Indeed, a reactive alpha-halogen acid may serve as a functional equivalent of an alpha-hydroxy acid byliberation of hydrochloricacid, nstead of water. such Such derivative can then radical. As to the manufacture of various esters from maleate, Example 1 is reacted with one l mole of lycoldmcmoleate, preferably in the' ab- Such compounds are the alpha-bromopalmitic acid,

. raw material or primary reactant.

CoMELETED MONOMERIC DERIVATIVE Example 2 The same procedure is followed as in Completed Monomeric Derivative, Example 1, preceding, except that the dimaleate described under the heading Oxyethylated glycerol maleate, Example 2 is used instead of the monomaleate.

COMPLETED MONOMERIC DERIVATIVE Example 3 The same procedure is followed as in the two preceding examples, except substituted for the monomaleate or dimaleate in the two preceding examples.

COMPLETED MONOMERIC DERIVATIVE Example 4 The same procedure is followed as in Examples 2 and 3, immediately preceding, except that for each pound mole of the dimaleate, or each pound mole of the trimaleate. instead of using one pound mole of ethylene glycol diricinoleate as a reactant, one employs two pound moles.

COMPLETED MONOMERIC DERIVATIVE Example 5 The same procedure is followed as in Example 3, preceding, except that for each pound mole of trimaleate, instead of adding one pound mole of ethylene glycol 'diricinoleate, one adds three pound moles of ethylene glycol diricinoleate for reaction.

COMPLETED MONOMERIC DERIVATIVE Example 6 Reference to the preceding that in each and glycerol (ratio 1 to examples will show every instance oxyethylated has been employed as a In the present instance, a more highly oxyethylated glycerol is elmployed, to wit, one involving the ratio of 1 o 8. ample 4, preceding.)

COMPLETED MONOMERIC DERIVA IVE Example 7 The same procedure is followed as in Example 6, immediately preceding, except that the oxyethylated glycerolemployed represents one having an even higher degree of oxyethylation. rFor example, one indicated by the ratio of 1 to- 21.

(See Oxyethylated glycerol maleate, Example 5, preceding.)

COMPLETED MONOMERIC DERIVATIVE. Example 8 The same procedure is followed as in Examples 1 to 'l, preceding, except that di-ethylene glycol diricinoleate is substituted for ethylene glycol ricinoleate.

COMPLETED MoNoMEEIc DERIVATIVE Example 9 The same. procedure is followed as in Examples 1 to 'l, preceding,except that C. and time of reacthat the trimaleate is (See Oxyethylated glycerol maleate, Ex-

dipropylene glycol 70 diricinoleate is substituted for ethylene glycol diricinoleate.

COMPLETED MONOMERIC DERIVATIVE Example 10 The same procedure is followed as in Examples 1 to 'l, preceding, except that glyceryi-alphamonomethyl ether diricinoleate is substituted for ethylene glycol diricinoleate.

The method of producing such fractional esters is well known. The general procedure is to employ a temperatur above the boiling point of y the pyrolytic point of the reactants. The products are mixed and stirred constantly during the heating and esteriflcation step. If desired, an inert gas, such as dried nitrogen or dried carbon dioxide, may be passed through the mixture. to add an esterification catalyst, such as sulfuric acid, benzen sulfonic acid, or the like. This is the same general procedure as employed in the manufacture of ethylene glycol dihydrogen diphthalate. (See U. S. Patent No. 2,075,107, dated March 30, 1937, to Frasier.)

Sometimes esterification is conducted most readily in the presence of an inert solvent, that carries away the water of esterification which may be formed, although, as is readily appreciated, such water of esterification is absent when such type of reaction involves an acid anhydride, such as maleic anhydride, and a glycol. However, if water is formed, for instance, when citric acid is employed, then a solvent such as xylene may be present and employed to carry oil? the water formed. The mixture of xylene vapors and water Vapors can be condensed so that the water is separated. The xylene is then returned to the reaction vessel for further circulation. This is a conventional and well-known procedure and requires no further elaboration.

In the previous definite tendency, in spite of precautions, at least in a number of instances, to obtain polymeric materials and certain cogeneric by-products. This is typical, of course, of organic reactions of thiskind, and as is well known, organic reactions per se are characterized by the fact that yields are the exception, rather than the rule, and that significant yields are satisfactory, especially in those instances where the by-products or cogeners may satisfactorily serve with the same purpose as the principal or intentional product. This is true in the present instance. In many cases when the compound is manufactured for purposes of demulsification, one is better off to obtain a polymer -in the sense previously described, particularly a polymer whose molecular weight is a rather small multiple of the molecular weight of the monomer, for instance, a polymer whose molecular weight is two, three, four, five, or six times the molecular weight of the monomer. Polymerization is hastened by the presence of an alkali, and thus, in instances where it -is necessary to have a maximum yield of the monomer, it may be necessary to take such precautions that the alkali used in promoting oxyethylation of glycerol, be removed before subsequent reaction.

clusive, no reference is made to the elimination of such alkaline catalyst, in View of the effectiveness of the low multiple polymers as demulsi- Sometimes it is desirable monomeric examples there is a and also polybasic acids of the kind herein contemplated.

With the above facts in mind, it becomes obvious that what has been previouslysaid, as to polymerization, with the suggestion that bymaterials were formed, may

of the type previously depolymers, or the heat-rethe same, and thus inscribed, or esterification arranged derivatives of .cluding the heat-rearranged derivatives of both the polymers and esteriflcation monomers, separately and joint Although the class of materials specifically contemplated in this instance is small and narrow class of a broad present series in their complete ramification, except in a manner employed in the hereto appended claims.

Although the products herein contemplated vary so broadly intheir characteristics, 1. e., monomers they may be added to the emulsion at the ratioof 1 part in'10,000, 1 part in 20,000, 1 part in 30,000, or for that matter, 1 part in 40,000. In such ratios must reside in 'interfacial position and the ability to usurp, preempt, tion previously occupied perhaps by the emulsifying colloid. In any event, reviewed in this light,

I the obvious common property running through the entire series; molecular size and apparent.

notwithstanding variation in physical make-up, Such statement is an obvious overradical, see what is said subsequently,

COMPLETED PoLYM nIc DERIVATIVES INCLUDING HEliT-REARRANGED 'COGENERS Example 1 is absolutely or replace the interfacial posi- COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED CocENERs Example 2 The same procedure is followed as in the preceding example, except that polymerization is continued, using'either a ture, or both, I molecular weight of approximately threeto four times that of the initial product.

COMPLETED POLYMERIC DERIVATIV S INCLUDING HEAT-REARRANGED CoGENERs Example 3 The same procedure is followed as in Examples 1 and 2, preceding, except that one employs as reactants a more highly oxy-ethylated glycerol and 'diethylene glycol diricinoleate, instead of ethylene glycol ricinoleate.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED CocENERs Example 4 The same procedure is followed as in Examples 1 to 3, preceding, except that one polymerizes a mixture instead of a sinrle monomer, for instance, a mixture of materials f the kind described in Completed monomeric derivative, Example 3, and

in Completed monomeric derivative, Example 4,

are mixed in molecular proportion and subjected to polymerization in the previous examples.

It is understood, of course, that the polymerized roduct need not be obtained as a result of a twostep procedure. -In other words, one need not manner indicated in the convert the'reactants into the monomer and then subsequently convert; the monomer into the polymer. The reactants may be converted through the polymer in one step. Indeed,

themonomer and polymerization may take place simultaneously. his is' especially true if polymerization is conducted in the absence of an inert solvent, xylene, as previously described, and if one uses a comparatively higher temperature, for instance, approximately 220 C. for polymerization. Thus, one pound mole of oxyethylated glycerol maleate'of the kind described, ratio lto 15, up to 1 to 21, is 'mixed with two moles of ethylene glycol diricinoleate and reacted for 30 hours at approximately 220 C, until the mass is homoand heat-rearcan be made in a single step,

illustrates a phenomenon which sometimes occurs either in such instances where alcoholic bodies of the kind herein illustrated are contem- One pound mole of oxyethylated glycerol diplated as reactants, or where somewhat kindred alcoholic bodies are employed. The reactants may be mixed mechanically to give a homogeneous mixture, or if the reactants do not mix to give a homogeneous mixture, then early in the reaction stage there is formed,'to a greater or lesser degree, sufllcient monomeric materials so that a weight approximately homogeneous system is present. Subsequently, as reaction continues, the system may become heterogeneous and exist in two distinct phases, one being possibly an oily body of moderate viscosity, and the other being a heavier material, which is sticky or sub-resinous in nature. In many instances it will be found that the thinner liquid material is a monomer and the more viscous or resinous material is a polymer, as previously described. Such product can be used for demulsification by adding a solvent which will mutually dissolve the two materials, or else, by separating the two heterogeneous phases and employing each as if it'were a separate product of reaction.

Conventional demulsifyi g agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water; petroleum hydrocarbons such as gasoline, kerosene, stove oil, a coal tar product such as benzene, toluene, xylene,, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents'. Similarly, the material or materials herein described, may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents, provided that such compounds are compatible. They will be compatible with the hydrophile type of solvent in all instances. Moreover, said material or materials may be used alone, or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents maybe used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oil and water-solub lity. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are sometimes used in a ratio of 1 to 10,000, or 1 to 20,000, or even 1 to 30,000, such an apparent insolubility in oil and water is not significant, because said reagents undoubtedly have solubility within the concentration employed. This same fact is true in regard to the material or materials herein described, except that they are invariably water-soluble.

We desire to point out that the superiority of the reagent or demulsifying agent used in our herein described process for breaking petroleum emulsions,.is based upon its ability to treat certain emulsions more advantageously and at a somewhat lower cost than is possible with other available demulsifiers, or conventional mixtures thereof. It is believed that the particular demulsifying agent or treating agent herein described will find comparatively limited application. so far as the majority of oil field emulsions are concerned; but we have found that such a demulsifying agent has commercial value. as it will economically break or resolve oil field emulsions in a number of cases which cannot be treated as easily or at so low a cost with the demulsifying agents heretofore available.

In practising our improved process for resolving petroleum emulsions of the water-in-oil type, a treating agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon'the emulsion to be treated,

in any of the various ways, or by any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used either alone, or in combination with other demulsifying procedure, such as the electrical dehydration process.

The demulsifier herein contemplated may be employed in connection with what is commonly known as down-the-hole procedure, 1. e., bringing the demulsifier in contact with the fluids of the well at the bottom of the well, or at some point prior to their emergence. This particular type of application is decidedly feasible when the demulsifier is used in connection with acidification of calcareous oil-bearing. strata, especially if suspended in or dissolved in the acid employed for acidification.

cognizance must be taken of the fact that the surface of the reacting vessel may increase or decrease reaction rate and degree of polymerization, for instance, an iron reaction vessel speeds up reaction and polymerization, compared with a glass-lined vessel.

As has been previously indicated, the sub-genus employed as an alcohol in the present instance is one of a series of alcoholic compounds which are contemplated in our co-pending applications Serial Nos. 447,151; 447,152; 447,153; 447,154; 447,155; 447,156; 447,157; 447,158; 447,160; 447,161; 447,162; 447,163; 447,164; 447,165; 447,166; 447,167 and 447,168, filed June 15, 1942.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the following formula:

coonm.

' basic carboxy acid having not over 8 carbon atoms; R1 is a water-insoluble polyhydric alcohol ester radical, the acyl radical of which being a high molal hydroxy aci-d acyl radical having at least 8 carbon atoms and not more than 32 carbon atoms; the alcohol radical of said ester radical having a valency of at least two and not more than 4, and said ester radical containing hydroxyl groups as part of the acyl radical only; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; 11. represents the numerals 2 to 4; n represents the numerals 3 to 10; n" represents the numerals 1 to 2; a: represents the numerals 0 to 2; 11 represents the numerals 0 to 2; .2 represents the numerals 1 to 3; 11: represents the numerals 0 to 1; and 11 represents the numerals 1 to 2.

2. A process for breaking petroleum emulsions of the water-in-oil-type, characterized by subjecting the emulsion to the action of a demulsifier comprising a member of the class consisting of monomers, sub-resinous esterification polymers,

alcohol radical ofsaid ester and cogenerlc'sub-resinous heat-rearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the'following formula:

in which R is a carboxyl-free radical of a dibasic carboxy acid having not over 6 carbon atoms; R1

atom equivalent including the acidic hydrogen n represents the numerals 2 to 4; n

atom itself; represents the numerals 3 to 10; 1: represents the numerals to 2; y represents the numerals 0 to 2; I

and z represents the numerals 1 to 3.

5. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifler is a water-insoluble polyhydric alcohol ester radical, the acyl radical of which being a high molal hydroxy acid acyl radical having at least 8 carbon atoms and not more than 32 carbon atoms;

the alcohol radical of said ester radical having a" valency of at least two and not more than 4, and said ester radical containing hydroxyl groups as part of the acyl radical only; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 2 to.4; n represents the numerals 3 to 10; .1: represents the numerals 0 to 2; 1 represents the numerals 0 to 2; and z represents the numerals 1 to 3.

3. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a member of the class consisting of monomers, sub-resinous esteriflcation polymers, and cogenericsub-resinous heatrearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the following formula:

[(CZHCCnn'OOCRCOOZJ; ClH&0 I lo)n'H]I (cimowoocncoonu. in which R is a carboxyl-free radical of a dibasic carboxyacid having not over 6 carbon atoms; R1

is a water-insoluble polyhydric alcohol ester radical, the acyl radical of which being a high molal hydroxy acid acyl radical having at least 8 carbon atoms and not more than 32 carbon atoms; the radical having a valency of at least 2 and not more than 4; and said ester radical containing hydroxyl groups as part of the acyl radical only; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 3' to 10; :2: represents the numerals 0, to 2; y represents the numerals 0 to 2; and .2 represents the numerals 1 to 3. f

4. A processfor breaking petroleum emulsicns of the. water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a polar member of the class consist ing of monomers, sub-resinous esteriflcation polymers, and cogeneric sub-resinous heatrearran'ged derivatives of the monomers and aforementioned polymers, separately and jointly, and of thefollowing formula:

ucimoh-oocncoozli minorminimal};

' cimowoocacooall.

in which R is a carboxyl-free radical of a dibasic carboxy acid having not over 6 carbon atoms; R1- is a water-insoluble polyhydric alcohol ester radi cal, the acyl radical of which being a high molal hydroxy acid acyl radical having-at least 8 carbon'atoms and not more than 32 carbon atoms; the alcohol radical of said ester radical having a valency of at least 2 and not more than 4, and said ester radical containing hydroxyl groups as part of the acyl radical only; Z is an acidic hydrogen comprising a polar acidic member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the following formul a uciniopoocacoozp cimoa-ucimowm.

[(CzHiQLyO 0 CBC OORI].

in which R is a carboxyl-free radical of a dibasic carboxy acid having not over 6 carbonatoms; R1 is a water-insoluble polyhydric alcohol ester radical, the acyl radical of which being a highmolal hydroxy acid acyl radical having at least 8 car- 'bon atoms and not more than 32 carbon atoms;

the alcohol radical of said ester radical having a valency of at least two and not more than 4, and said ester radical containing hydroxyl groups as part of the acyl radical only;'-Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents-the numerals 3- to 10; :i: represents the numerals 0 to 2; y represents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

6. A process for breaking petroleum emulsions of the waterin-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a polar acidic member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heatrearranged derivatives of .the monomers and aforementioned polymers, separately and jointly, and of the following formula:

[(C2H50)1HOOCBCOOR1]I in which R is a carboxyl-free radical of a dibasic carboxy acid having not-over 6 carbon atoms; R1 is a water-insoluble diol ester radical in which the acyl radicals contain 18 carbon atoms and at least one hydroxyl radical; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 3 to 10; :1: represents the numerals 0 to 2; 1! represents the numerals 0 to 2; numerals 1 to 3.

"I. A process for breaking petroleum emulsions of the water-in-oil type, characterizedby subjecting the emulsion to the action of a demiilsifier comprising a polar acidic member of the class consisting of monomers, subus esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives of the monomers and aforementioned polymers, separately and jointly,

and 2 represents the sents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

8. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifler comprising a polar acidic member of the class consisting of monomers; sub-resinous esteriflcation polymers, and cogeneric sub-resinous heat-rearranged derivatives of the monomers and aforementioned jointly, and of the following formula.

l(c,mo)..'oocncooz l.'

CHlOtKGtHlOhl' warm-000110001111.

polymers, separately and 10 in which R is a carboxyl-free radical of a dibasic carboxy acid having not over 6 carbon atoms; R1 is an ethylene glycol diricinoleate radical; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 3 to 10; :1: represents the numerals 0 to 2; 11 represents the numerals 0 to 2; and z represents the numerals 1 to 3.

MELVIN DE GROOTE. BERNHARD KEISER. 

